CN102473753A - Glass substrate with conductive film for solar cell - Google Patents

Glass substrate with conductive film for solar cell Download PDF

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Publication number
CN102473753A
CN102473753A CN201080032233XA CN201080032233A CN102473753A CN 102473753 A CN102473753 A CN 102473753A CN 201080032233X A CN201080032233X A CN 201080032233XA CN 201080032233 A CN201080032233 A CN 201080032233A CN 102473753 A CN102473753 A CN 102473753A
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glass substrate
conducting film
solar cell
film
buckling deformation
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泽田正弘
永金知浩
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2453—Coating containing SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2456—Coating containing TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/211—SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C03C2217/241—Doped oxides with halides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Disclosed is a glass substrate with a conductive film, which does not easily cause fluctuations in power generation and can be excellently encapsulated with an encapsulation material when used in a thin solar cell. Specifically disclosed is a glass substrate with a conductive film for a solar cell, which is obtained by forming a conductive film on a glass substrate that has a thickness of 2 mm or less. The glass substrate with a conductive film for a solar cell is characterized in that the warping deformation (W) of the glass substrate represented by the formula below is 0.5 [mu]m/cm2 or less. W = D/L2 (D represents the maximum warp ([mu]m) of the glass substrate, and L represents the diagonal length (cm) of the glass substrate).

Description

The glass substrate of used for solar batteries band conducting film
Technical field
The present invention relates to the glass substrate of used for solar batteries band conducting film.In particular to as the electrode base board that in solar cell, uses preferably with the glass substrate of conducting film.
Background technology
In recent years, increasingly high for the demand of solar cell that with monocrystaline silicon solar cell, polysilicon solar cell or non-crystal silicon solar cell is representative.These solar cells mainly utilize in home-use generating, commercial usefulness generating etc.In addition, as other solar cell, developed CIS solar cell, CdTe solar cell, dye-sensitized solar cell, organic thin film solar cell etc., these batteries are also just in practicability.
In solar cell,, can use the glass substrate of band conducting film as electrode base board.At this, as glass substrate, since favourable aspect manufacturing cost and versatility, soda-lime glass generally used.And, use fluorine-doped tin oxide (FTO), tin-doped indium oxide nesa coatings such as (ITO) as conducting film.Wherein, Though it is relatively poor that FTO and ITO compare resistivity; But stable aspect chemical property and hot property, and can also expect the effects such as conductivity raising that light that the concaveconvex shape by the film surface causes is sealed effect up for safekeeping and caused by the increaseization of surface area, therefore; Can be widely used as the electrode base board (for example, with reference to patent documentation 1 and non-patent literature 1) that dye-sensitized solar cell and non-crystal silicon solar cell are used.
Usually, in the making of FTO film, good and cost Di is adopted thermal cvd (hot CVD) method from film forming.Particularly, the mist through making the compound that contains tin and fluorine produces pyrolysis and film forming being heated on about glass substrate more than 400 ℃.Need to prove, have in the hot CVD method in the plate glass manufacturing line, utilize its heat and the online CVD method of film forming and the cooled glass-cutting of will going ahead of the rest for the size of regulation, heat the off-line CVD method of film forming again.
Yet,,, except battery in the past, also use solar cell as its power supply along with popularizing of in recent years mancarried electronic aid.Be used at solar cell under the situation of mancarried electronic aid, require than home-use generating that is provided with outside the room that is used in the past or commercial solar cell slimming and lightweight further with generating.Particularly the energy conversion efficiency of dye-sensitized solar cell under room light compared highlyer with solar cells made of crystalline silicon, and therefore, its demand is also increasing.
Dye-sensitized solar cell by: the band conducting film glass substrate; Be formed on the oxide semiconductor porous electrode on the glass substrate of being with conducting film by oxide semiconductor porous layer (mainly being titanium oxide layer) formation; Be adsorbed on the pigments such as Ru pigment on this oxide semiconductor porous electrode; The iodine electrolyte that contains iodine; Be formed with catalyst film and conducting film to formations such as electrode base boards.At this; For the glass substrate that prevents to be filled in the band conducting film and leakage, be with the glass substrate of conducting film and the neighboring of electrode base board is sealed with resin or with encapsulants such as low-melting glass such as lead glass, bismuth borate glasses the iodine electrolyte between the electrode base board.
[prior art document]
Patent documentation 1: the spy of Japan opens the 2002-260448 communique
Non-patent literature 1: " electrically conducting transparent membrane technology " (revising the 2nd edition), Japanese OHM company (オ one system society) publishes, the 153rd～165 page
Summary of the invention
The problem that invention will solve
When reducing to realize the slimming of solar cell with the thickness of the glass substrate of conducting film, different with the solar cell in the past that does not have slimming, be easy to generate the fluctuation of generating, on solar battery panel, be difficult to obtain uniform generating state.In addition, the glass substrate of band conducting film in the past exists the problem of the sealing difference of encapsulant, for example, in dye-sensitized solar cell, the unfavorable conditions such as leakage of iodine electrolyte takes place easily.
Therefore, the objective of the invention is to, be provided under the situation that is used for slim solar cell the glass substrate of the good band conducting film of the sealing of the fluctuation that is difficult for taking place generating, encapsulant.
Solve the means of problem
The inventor etc. have carried out deep research, and the result confirms: the reason of the fluctuation of the generating that produces during slimization of solar cell is the buckling deformation with the glass substrate of conducting film.Find thus: the buckling deformation of the glass substrate through will the band conducting film limits within the specific limits, can solve above-mentioned problem, thereby propose the present invention.
That is, the present invention relates to a kind of glass substrate of used for solar batteries band conducting film, it is on the glass substrate below the thickness 2mm, to form conducting film and obtain, and it is characterized in that, the buckling deformation amount W of the glass substrate of being represented by following formula is 0.5 μ m/cm 2Below.
W＝D/L 2
D: the maximum set-back of glass substrate (μ m), L: the diagonal of glass substrate (cm)
In the present invention; Buckling deformation amount W is meant: will carry with the glass substrate of conducting film when putting on platform as top with the conduction face, poor (the maximum set-back of glass substrate) of maximum and minimum value of height that with the flat surface is benchmark is divided by square value that obtains of the diagonal of glass substrate.The set-back of glass substrate can be measured through linearity analyzer that can carry out elevation measurement or the angularity analyzer that has utilized laser etc.
When on glass substrate, forming conducting film,,, thereby be easy to generate buckling deformation in the inner generation of glass substrate strain because the thermal coefficient of expansion of glass substrate and conducting film is poor.The glass substrate of the band conducting film that the thickness that uses in the solar cell in the past is big, because mechanical strength is big, therefore, the problem of buckling deformation is fewer.But under the situation of thin thickness of the glass substrate of band conducting film, particularly thickness reaches 2mm when following, and buckling deformation will increase.In case buckling deformation increases, cause obstacle in the operations such as film forming that will be when the cell (セ Le) of solar cell is made or printing, sealing, assembling.
For example, dye-sensitized solar cell generally is employed in the structures of under the state of the substrate gap (cell gap) that keeps certain the glass substrate of 2 band conducting films being fitted.But, when on substrate, producing big buckling deformation, becoming difficulty owing to fit, it is uncertain that substrate gap becomes.Therefore, on solar battery panel, generating produces fluctuation.
In addition; In the production process of dye-sensitized solar cell, owing to use silk screen print method to be applied on the glass substrate of band conducting film, therefore as the titanium oxide paste of its electric layer; When on the glass substrate of band conducting film, producing big buckling deformation, just be easy to generate crawling.The crawling of titanium oxide paste also becomes the reason of generating fluctuation.
In addition, encapsulants such as resin, low-melting glass use silk screen print method to be applied on the glass substrate of band conducting film.Therefore, when on the glass substrate of band conducting film, producing big warpage, will produce crawling, thus the sealing variation.For example, in dye-sensitized solar cell, be easy to generate the unfavorable conditions such as leakage of iodine electrolyte.
The glass substrate of used for solar batteries band conducting film of the present invention is set in the above-mentioned scope through the buckling deformation amount W with glass substrate; Can eliminate above problem; The generating that as far as possible suppresses on solar battery panel fluctuation is provided; Realize uniform generating state, and the glass substrate of the good band conducting film of the sealing of encapsulant can be provided.
The second, the glass substrate of used for solar batteries band conducting film of the present invention, preferred conduction film are the conducting films that is made up of fluorine-doped tin oxide.
As stated; Owing to the conducting film (FTO film) that constitutes by fluorine-doped tin oxide; Stable aspect chemical property and hot property; Can also expect the effects such as conductivity raising that light that the concaveconvex shape by film surface causes is sealed effect up for safekeeping and caused by the increase of surface area, therefore, be particularly suitable for the electrode base board of using as dye-sensitized solar cell and non-crystal silicon solar cell.
The 3rd, the glass substrate of used for solar batteries band conducting film of the present invention, the thermal coefficient of expansion that is preferably glass substrate is 60～85 * 10 -7/ ℃.
Be limited in the above-mentioned scope through thermal coefficient of expansion glass substrate, thermal coefficient of expansion easily and titanium oxide and collector electrode, sealing with other parts match such as low-melting glasses.Consequently, be difficult for to produce problem because of peeling off of causing of thermal coefficient of expansion inconsistent or crackle.In addition, can reduce the membrane stress that produces between conducting film and the glass substrate, suppress the buckling deformation of glass substrate.
Need to prove that in the present invention, the thermal coefficient of expansion of glass substrate is meant the thermal coefficient of expansion in 30～380 ℃ the scope of measuring based on JIS R3103.
The 4th, the glass substrate of used for solar batteries band conducting film of the present invention, preferably the buckling deformation amount W of the glass substrate after 500 ℃, 30 minutes heat treated is 0.5 μ m/cm 2Below.
The glass substrate of band conducting film offers heat treated sometimes in the production process of solar cell.For example, in the production process of dye-sensitized solar cell, can carry out the calcining of titanium oxide paste etc.The buckling deformation of the glass substrate of the band conducting film after the heat treated is compared with the substrate before the heat treated, and tendency more significantly becomes.According to the present invention, even after 500 ℃, 30 minutes heat treated, because the buckling deformation amount W of glass substrate satisfies above-mentioned scope, therefore, the uniformity of the generating state on the solar battery panel and the sealing of encapsulant are very good.
The 5th, the glass substrate of used for solar batteries band conducting film of the present invention is characterized in that, the buckling deformation amount W of the glass substrate after 550 ℃, 30 minutes heat treated is 0.5 μ m/cm 2Below.
The 6th, the glass substrate of used for solar batteries band conducting film of the present invention, the strain point of preferred glass substrate are more than 525 ℃.
Be limited in the above-mentioned scope through strain point,, also can suppress the buckling deformation that produces because of structural relaxation that heat treated causes even under the inner situation that produces stress of glass substrate with glass substrate.
Need to prove that the strain point of glass substrate is meant the value of measuring based on JIS R3103 among the present invention.
The 7th, the glass substrate of used for solar batteries band conducting film of the present invention, preferred solar cell is a dye-sensitized solar cell.
Description of drawings
Fig. 1 is used to explain that the glass substrate of band conducting film produces the sketch map of the mechanism of buckling deformation owing to the influence of membrane stress.
Fig. 2 is used to explain that the influence of the residual stress that produces after glass substrate is owing to glass annealing produces the sketch map of the mechanism of buckling deformation.
Fig. 3 is the sketch map that the influence of the structural relaxation that produces after owing to heat treated of the glass substrate that is used to explain the band conducting film produces the mechanism of buckling deformation.
Symbol description
1 glass substrate
2 conducting films
The C compression
The T tensile stress
Embodiment
In the present invention, the buckling deformation amount W of glass substrate is 0.5 μ m/cm 2Below, be preferably 0.4 μ m/cm 2Below, be preferably 0.3 μ m/cm especially 2Below.When the buckling deformation amount W of glass substrate surpasses 0.5 μ m/cm 2The time, when the glass substrate subtend of 2 band conducting films is fitted, substrate gap (cell gap) is remained the difficulty that necessarily will become, perhaps will be easy to generate the crawling of titanium oxide paste, thereby become the reason of generating fluctuation.And same, the encapsulants such as resin and low-melting glass that are coated on the glass substrate also are easy to generate crawling, thereby might cause seal defect.
Need to prove, for example when dye-sensitized solar cell is made, carry out behind the calcination process that is fitted in titanium oxide paste layer of the glass substrate of 2 band conducting films.Therefore, the glass substrate of band conducting film of the present invention, preferably the buckling deformation amount W behind this calcination process satisfies above-mentioned scope.Particularly, the glass substrate of band conducting film of the present invention, the buckling deformation amount W of the glass substrate after 550 ℃, 30 minutes heat treated is 0.5 μ m/cm 2Below, be preferably 0.4 μ m/cm 2Below, be preferably 0.3 μ m/cm especially 2Below.
Below, the mechanism of buckling deformation of the glass substrate of band conducting film is described.
The influence of the residual stress that produces in the influence of the membrane stress that the thermal expansion difference of the main conducting film during with (a) film forming of the buckling deformation of the glass substrate of band conducting film and glass substrate causes, the glass substrate after (b) glass annealing and (c) during the solar cell making, the influence of the structural relaxation that glass substrate is carried out produce after the heat treated has relation.
(a) influence of membrane stress
Membrane stress when usually, on glass substrate, forming conducting film is represented by following formula (1).
σ＝E×(α s-α f)×(T d-T r) (1)
σ: membrane stress, E: the Young's modulus of conducting film, α s: the thermal coefficient of expansion of glass substrate
α f: the thermal coefficient of expansion of conducting film, T d: film-forming temperature, T r: room temperature
At this, the Young's modulus of conducting film and thermal coefficient of expansion are got the intrinsic value of each conductive film formed, and hence one can see that, and membrane stress depends on the thermal coefficient of expansion and the film-forming temperature of substrate.For example, the thermal coefficient of expansion of known FTO film is 35 * 10 -7/ ℃ (Solar Energy Materials and Cells 49 (1997) 107-112).On the other hand, in the dye-sensitized solar cell employed glass substrate to use thermal coefficient of expansion usually be 60～85 * 10 -7/ ℃ the glass substrate of scope, therefore, this glass substrate is compared with the FTO film, thermal coefficient of expansion increases.Therefore, on the interface of FTO film and glass substrate, producing compression in FTO film side, and produce tensile stress in the glass substrate side, is upper surface with the FTO film, and the glass substrate buckling deformation is convex (with reference to Fig. 1).Need to prove that under the enough thick situation of the thickness of glass substrate, with respect to membrane stress, the elasticity of substrate is had the advantage, and therefore, can not produce buckling deformation.
The influence of the residual stress that (b) produces in the glass substrate after the glass annealing
In the manufacturing process of plate glass, melten glass through float glass process etc. be configured as tabular after, in annealing furnace, carry out glass annealing.Usually, the cooling rate of the surface element of glass substrate is fast, and the cooling rate of central part is slow, therefore, even after glass annealing, because this cooling rate is poor, though residual stress is very little, still has the tendency of generation.At this moment, at the surface element of glass substrate, compression works, and at central part, tensile stress works.The thickness of glass is bigger or cooling rate is big more, and these stress are big more.This be because, on the thickness direction of glass substrate, be easy to generate Temperature Distribution.
In addition, in film formation process, online CVD method is a film forming under the temperature more than the strain point of glass substrate; Off-line CVD method is a film forming under glass substrate being heated near the state of the temperature of strain point.Therefore, if not fully annealing after film forming then as stated, will produce the different residual stresss that cause because of cooling rate between the surface element of glass substrate and central part.
Like this, in the film formation process of the manufacturing process of glass substrate or conducting film, comprise the refrigerating work procedure that starts from heated condition.For example,,, then become and encourage diastrophic reason (with reference to Fig. 2) not under the square one in the cooling rate in the table of glass in case stress equilibrium is broken.
In addition; Under the state that has residual stress on the glass substrate; When the glass of grinding in order to make the thickness of glass attenuation with the conducting film opposition side, owing to be removed with the compression generation portion of the glass surface of conducting film opposition side, therefore; Residual stress distribution at the thickness direction of glass substrate will produce bias voltage, thereby produce big buckling deformation.Therefore, the amount of grinding on glass substrate behind the formation conducting film is preferably below 1/4 for below 1/2 of thickness before grinding, and does not more preferably grind.
The influence of the structural relaxation that (c) glass substrate is carried out producing after the heat treated
As stated, in the glass substrate after the conducting film film forming, usually exist to result from the residual stress of membrane stress.When the glass substrate of the band conducting film that has residual stress being offered the heat treated in the production process of solar cell, will cause the structural relaxation of glass, residual stress changes.At this moment, glass substrate because above-mentioned membrane stress produces tensile stress, therefore, is difficult to cause the contraction that structural relaxation causes on the interface of itself and conducting film.On the other hand, with the face of conducting film opposition side on, almost do not have the influence of membrane stress, therefore, promote the contraction that structural relaxation causes easily.Thus, the conducting film side generation compression at glass substrate produces tensile stress at opposition side, is under the situation of FTO film at conducting film particularly, encourages buckling deformation (with reference to Fig. 3) easily.
Need to prove that the viscosity of glass is low more, be easy to generate the structural relaxation that causes by heat treated more.At this, the viscosity of glass depends on strain point, and strain point is big more, and viscosity is high more, is difficult to produce structural relaxation more, as a result of, is difficult to produce buckling deformation more.From such viewpoint, the strain point of glass substrate is preferably more than 525 ℃, is preferably especially more than 550 ℃.
In the present invention, the thickness of glass substrate is below the 2mm, is preferably below the 1.8mm, more preferably below the 1.5mm, is preferably below the 1.2mm especially.Under the situation of thickness greater than 2mm of glass substrate, be difficult to realize the slim lightweight of solar cell.On the other hand, when the thickness of glass substrate was too small, though flexibility (flexible) is good, intensity reduced, and is damaged easily.Therefore, the following of the thickness of glass substrate is limited to more than the 0.05mm, is preferably more than the 0.1mm, is preferably more than the 0.2mm especially.
As conducting film, can enumerate: fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO) etc.
The thickness of conducting film is preferably regulated in the scope of 0.4～1.5 μ m.When the thickness of conducting film is lower than 0.4 μ m, be difficult to obtain sufficient conductivity.On the other hand, when the thickness of conducting film surpasses 1.5 μ m, have membrane stress and become tendency big, that buckling deformation increases.And, make easily and reduce with respect to the transmitance reduction of sunlight spectrum, the generating efficiency of solar cell.
The resistance value of conducting film is preferably 25 Ω/below the, more preferably 15 Ω/below the.When resistance value surpassed 25 Ω/, the conductivity with film reduced, as the tendency of Solar cell performance variation.
The average surface roughness of conducting film (Ra) is preferably more than the 20nm, more preferably more than the 30nm.Be set in this scope through average surface roughness, can when performance light is sealed effect up for safekeeping, increase the surface area of film, improve conductivity film.
For example, the raw material as the FTO film that passes through film build methods such as hot CVD method as Xi Yuan, can use SnCl 4, C 4H 9SnCl 3, (CH 3) 2SnCl 2As the fluorine source, can use HF, CF 3COOH, CHF 2, CCl 2F 2Deng.
In the present invention, the film-forming temperature of conducting film is 400～650 ℃, is preferably 400～600 ℃, is preferably 420～570 ℃ especially.When film-forming temperature was lower than 400 ℃, it is slow that film forming speed became, and the remarkable variation of productivity ratio is therefore unrealistic.When film-forming temperature surpassed 650 ℃, according to above-mentioned formula (1), it is excessive that membrane stress becomes, and particularly glass substrate is thinned to 2mm when following, is easy to generate buckling deformation.
Need to prove, under the situation that glass substrate is made up of the glass that contains alkali metal oxide, can between conducting film and glass substrate, SiO be set 2Etc. undercoating.Through such undercoating is set, can prevent that the conductivity of the FTO film that the alkali metal ion of stripping causes from glass from reducing.
In the present invention, the thermal coefficient of expansion of glass substrate is 60～85 * 10 -7/ ℃, be preferably 70～85 * 10 -7/ ℃, be preferably 75～85 * 10 especially -7/ ℃.The thermal coefficient of expansion of glass substrate is lower than 60 * 10 -7/ ℃ the time since with inconsistent with the thermal coefficient of expansion of other parts such as low-melting glass of titanium oxide and collector electrode, sealing, be easy to generate peeling off and crackle of these parts.On the other hand, the thermal coefficient of expansion of glass substrate surpasses 85 * 10 -7/ ℃ the time, through above-mentioned formula (1), it is excessive that membrane stress becomes, and particularly is thinned to 2mm when following at glass substrate, is easy to generate buckling deformation.
Need to prove; Be applied at glass substrate under the situation of dye-sensitized solar cell band conducting film of the present invention; In the production process of this dye-sensitized solar cell, the calcination process, sealing that exists titanium oxide paste and collector electrode all is the heating treatment step of about 500～550 ℃, time carrying out with the sealing process of low-melting glass etc.For example, the calcining of titanium oxide paste is to be the operation of purpose to improve electronic conductivity, is carrying out under 480～580 ℃ of heat bonding each other between the Titanium particles.When calcining heat was lower than 480 ℃, the heat bonding of Titanium particles (necking down) became insufficient easily.On the other hand, when improving owing to calcining heat, the fusion area between the Titanium particles increases; Therefore, conductive path increases, however; When calcining heat surpasses 580 ℃, the tendency that the heat bonding that exists Titanium particles excessively carries out, the specific area of Titanium particles reduces, or Titanium particles changes the tendency of rutile-type into from Detitanium-ore-type; Therefore, energy conversion efficiency reduces easily.
Embodiment
Below, the present invention will be described based on embodiment, but the present invention is not limited to these embodiment.
(embodiment 1～5)
The glass substrate of the characteristic of record, thickness in having table 1 (on 250 * 250mm), forms the FTO film through the hot CVD method.Particularly, use (CH as raw material 3) 2SnCl 2, CF 3COOH earlier with they gasifications, with its glass substrate that blows to the film-forming temperature that is heated to table 1 record, carries out film forming then thus, obtains the glass substrate with conducting film.For the thickness that makes the FTO film reaches about 1 μ m, in 2～5 minutes scope, regulate film formation time.Carry out glass annealing with 20 ℃/minute after the film forming.
The glass substrate of resulting band conducting film is cut into 150 * 200mm, measure the buckling deformation amount.About embodiment 2, be that the face with conducting film formation face opposition side is ground behind the thickness that reaches regulation, measure the buckling deformation amount.
The buckling deformation amount is to carry through the glass substrate with the band conducting film after the glass annealing to put on platform; Measure maximum buckling deformation amount through linearity analyzer (Fujita Seisakusho K.K.'s system), with this maximum buckling deformation amount divided by the diagonal of glass substrate square and calculate.
Then, the glass substrate of band conducting film is implemented 500 ℃, 30 minutes heat treated, the buckling deformation amount after the mensuration glass annealing.The heat treated curve of this moment is with 10 ℃ of/minute intensifications, with under 2 ℃ of/minute coolings.In addition, about embodiment 5, the substrate of having implemented 550 ℃, 30 minutes heat treated is also measured.
In addition, the glass substrate of being with the FTO film is cut into 150 * 200mm, use 200 purpose silk screens that titanium oxide paste (SOLARONIX society, Ti-Nanoxide D/SP) is carried out silk screen printing with width 5mm, length 180mm above that.Naked eyes are confirmed the titanium oxide layer after the silk screen printing, will be " zero " to the average evaluation of whole even printing of glass substrate, with confirming that having the position of not printing or the average evaluation of obvious crawling is " * ".The result is shown in table 1.
Then, evaluation sealing as follows.
The glass substrate of band FTO film is divided equally, cut into the size of 75 * 100mm, on the FTO face of a glass substrate circumference, use distributor coating UV cured resin therein.The discharge rate of at this moment, regulating the UV cured resin with the mode that reaches live width 5mm, the about 100 μ m of thickness after the sealing.Then, with FTO face mode respect to one another, make another substrate and the substrate subtend that is coated with this UV cured resin, irradiation UV light carries out the bonding of two glass substrates.The perusal stick portion with not existing not bond site and the good situation of sealing state to be made as " zero ", is made as " * " with observing the situation that not bonding position etc. produced poor sealing.
(comparative example)
The glass that is opposition side with FTO film formation face to the glass substrate (Nippon Sheet Glass Co Ltd's system) of the commercially available band FTO film of 150 * 200 * 4mm is ground, until reaching thickness 1.1mm.Glass substrate to the band FTO film after grinding is measured the buckling deformation amount.
Then, the glass substrate of the band FTO film after grinding is implemented 500 ℃, 30 minutes heat treated, measure the buckling deformation amount after annealing.The heat treated curve of this moment is with 10 ℃ of/minute intensifications, with 2 ℃ of/minute coolings.In addition, the substrate of having implemented after 550 ℃, 30 minutes the heat treated is likewise measured.
According to the method same with embodiment, on the glass substrate of band FTO film, the titanium oxide paste is carried out silk screen printing, confirm printing.In addition, estimate similarly about sealing.The result is shown in table 1.
Table 1
Figure BDA0000131583950000131
Can be known that by table 1 in embodiment 1～5, the buckling deformation amount of the glass substrate of band FTO film is little, the printing of titanium oxide paste and sealing are all good.On the other hand, in comparative example, the thermal coefficient of expansion of glass substrate is big, and the strain point of glass is also very low, and therefore, the buckling deformation amount before the heating is 0.6 μ m/cm 2, the buckling deformation amount after heating under 500 ℃ is 1.0 μ m/cm 2, the buckling deformation amount after 550 ℃ of heating is greatly to 3.2 μ m/cm 2Therefore, both had the even position and a part of position that is not printed of crawling of titanium oxide paste, printing is also very poor.And sealing is also very poor.
Although be particularly and with reference to specific execution mode describe the present invention, very clear and definite to those skilled in the art is, only otherwise break away from the spirit and scope of the present invention, also can add various changes and correction.
Japanese patent application that the application proposed based on July 24th, 2009 (the special 2009-173342 of hope) and the Japanese patent application (the special 2010-157886 of hope) that proposed on July 12nd, 2010, its content is herein incorporated by reference.

Claims (7)

1. the glass substrate of a used for solar batteries band conducting film, this glass substrate forms conducting film and obtains on the glass substrate below the thickness 2mm, it is characterized in that, and the buckling deformation amount W of the glass substrate of being represented by following formula is 0.5 μ m/cm 2Below,
W＝D/L 2
Wherein, D is the maximum set-back of glass substrate, and unit is μ m; L is the diagonal of glass substrate, and unit is cm.
2. the glass substrate of used for solar batteries band conducting film as claimed in claim 1 is characterized in that, said conducting film is the conducting film that is formed by fluorine-doped tin oxide.
3. according to claim 1 or claim 2 the glass substrate of used for solar batteries band conducting film is characterized in that the thermal coefficient of expansion of said glass substrate is 60～85 * 10 -7/ ℃.
4. like the glass substrate of each described used for solar batteries band conducting film in the claim 1～3, it is characterized in that after 500 ℃, 30 minutes heat treated, the buckling deformation amount W of said glass substrate is 0.5 μ m/cm 2Below.
5. like the glass substrate of each described used for solar batteries band conducting film in the claim 1～3, it is characterized in that after 550 ℃, 30 minutes heat treated, the buckling deformation amount W of said glass substrate is 0.5 μ m/cm 2Below.
6. like the glass substrate of each described used for solar batteries band conducting film in the claim 1～5, it is characterized in that the strain point of said glass substrate is more than 525 ℃.
7. like the glass substrate of each described used for solar batteries band conducting film in the claim 1～6, it is characterized in that said solar cell is a dye-sensitized solar cell.
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